DE1595628A1 - Compounds with two or more acetoacetic ester groups - Google Patents

Description

FARBT.'ERKE HOECHST AG. formerly Master Lucius & Brüning

File number: Fw 500C

Date: June 6, 1969

Dr B / Dlt

Process for the preparation of compounds having two or more acetoacetic ester groups

It is known that aliphatic, cycloaliphatic or aromatic compounds containing hydroxyl groups can be used with diketene can convert to acetoacetic acid esters. This reaction will carried out in the presence of acidic, basic or metallic catalysts in order to accelerate the reaction rate and to reduce the proportion of polymeric diketene. It has proven to be advantageous to use mixtures as catalysts from organic acids and bases to vex *, in particular mixtures of acetic acid and sodium acetate and Acetic acid and tertiary aliphatic amines. (German patent 717 652 and USA patent 2 351 366).

There is also a method of making aliphatic Monoacetoacetic acid esters known, in which one monohydric aliphatic alcohols in the presence of 1,4-diazabicyclooctane reacts as a catalyst with diketene. (Chem. Abstacts, volume (1965) columns 14 505/6).

In this process, however, you have to work under very mild conditions and in very great dilution, with as Diluent either an excess of the alcohol or an inert solvent such as ether, acetone, or ethyl acetate Benzene, must be used. The disadvantage of this process is that you have to clean the Acetoacetic ester obtained from the solvent or excess alcohol and the residue, which from dark

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colored polymeric products and accounts for about 5 - 7% of the total yield, distill off nut.

For the preparation of compounds with two or more acetoacetic ester groups which cannot be distilled and therefore cannot be separated from polymeric by-products, the reaction must, however, be carried out as quantitatively as possible will. In addition, the execution of the reaction in a solvent means, which under certain circumstances only very difficult to remove quantitatively, not only an additional technical effort, but quality and appearance of the product suffer considerably, since side reactions are caused when acetoacetic esters are heated over a long period of time can take place that lead to severe discoloration.

Surprisingly, it has now been found that the abovementioned Difficulties in the preparation of compounds with two or more acetoacetic ester groups can be avoided if one aliphatic ^ containing at least two hydroxyl groups, cycloaliphatic or araliphatic compounds in the presence of 0.0001-1 percent by weight, preferably 0.001 0.1 Weight percent, 1,4-diaza- (2,2,2) -bicyclooctane based on the amount of hydroxyl compound used, reacts with diketene in the absence of solvent.

The optimum reaction temperature to be used in the acetoacylation according to the invention in the individual case is determined in particular by the catalyst concentration used, the type of compound to be aeylated and the process carried out, which can be discontinuous or continuous. In most cases, one works at convenient temperatures of between 20 ° and 120 ⁰ C, preferably-between 50 and 80 ° C.

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The veriahrensgonigte implementation can be in the presence of a organic acid. Examples of such Acids are in particular acetic acid, which is usually the case with the The technical diketene used is anyway incorporated into the reaction mixture, as well as propionic acid and butyric acid. The amount of acid generally does not exceed that about five times the molar amount of the tertiary diamine used. Diketene and Hydro? R.yl compound are generally roughly used stoichiometric ratio used.

Due to the high reaction rate of the catalysed by 1,4-diaza- (2,2,2) -bicyclooctane Acetoacylierung the highly exothermic reaction can be even in the absence of diluents of diketene with di- and polyhydroxy compounds in the temperature range between 50 ° and 8O ⁰ C by external cooling comfortably / control that large amounts can be converted within a short time without a dangerous accumulation of diketene. Due to the low catalyst concentrations required for the conversion, no by-products such as dehydroacetic acid or polymeric diketene occur in this procedure and when using pure diketene. The almost water-white reaction products represent pure compounds with two or more acetoacetic ester groups after "" removing any small excess of diketene present by applying a vacuum , 6 % acetic acid. The products could not previously be manufactured in this purity.

According to the invention, aliphatic compounds are used as starting compounds cycloaliphatic and aliphatic hydroxy compounds in Consider, which have a molecular weight up to about 5000 and, depending on the molecular weight, can contain up to about 50 hydroxyl groups in the molecule. The hydrocarbon residues These compounds can also be replaced by heteroatoms, such as, in particular, oxygen or nitrogen atoms, or by carbon

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acid ester groups be interrupted one or more times "

Particular mention may be made of simple aliphatic and alicyclic diols and triols, such as ethylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methyl-pentadiol-2,4, cyclohexanediol-1,2, cyclohexanediol-1,3, cyclohexanediol 1,4-1,4-dihydroxyraethylene cyclohexane, bis-4,4 ^l -h5'droxycyclohexyl-l, l-dimethyl-methane, bis-4,4 ^t -hydroxycyclohexyl-methane, 1,1,1-trimethylolethyl, 1 , 1,1-triraethylolpropane,!, L-bis-hydroxy-methylene-cyclohexane-S »

Araliphatic compounds that may be mentioned are 1,4-dihydroxymethylene benzene. Examples of ethers and polyethers containing hydroxyl groups are diethylene glycol, dibutylene glycol, polymeric linear propylene oxides with a molecular weight of 400-2000, ethoxylated and propoxylated hydroxyl compounds, such as, in particular, propoxylated trimethylolpropane with a molecular weight of 300-4500 and propoxylated polyesters with a molecular weight of 400-600 linear polyesters of adipic acid and maleic acid may be mentioned. Fumaric acid with diols or ether diols, such as 1,4-butanediol, diethylene glycol or dibutylene glycol or ethoxylated 4,4 ^f -dihydroxyphenyldimethylene methane and also branched polyesters of adipic acid and phthalic acid with the above-mentioned diols with the addition of glycerol or trimethylolpropane a molecular weight of 300-4000 into consideration.

There may also be mentioned tertiary amines containing hydroxyl groups, in particular ethoxylated or propoxylated amines, such as triethanolamine, N, N'-tetra- (2-hydroxyethyl) -ethylenediamine, N, N ¹ -tetra- (2-hydroxypropyl) -ethylene-diamine, N ^ , Ng ι Ng-penta- (2-hydroxypropyl) -diethylenetriamine, N, N ^f -Tetra- (2-hydroxypropyl) -diaminopropane, N, N'-tetra- (2-hydroxypropyl) -hexamethylenediamine, tetra- (2- Hydroxypropyl) di-3-aminopropyl) methylamine and penta- (2-hydroxypropyl) di-3-aminopropylamine.

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The compounds obtainable according to the method with two or more acetoacetic ester groups, which are predominantly new compounds, and which so far only were very difficult to produce by transesterification, can be used as intermediates for the production of optionally foamed Plastics are used.

The products available according to the process are still as Light stabilizers and plasticizers suitable for plastics.

In the following examples, parts mean parts by weight and percent weight percent,

example 1

1078 parts of diketene were added dropwise to 636 parts of diethylene glycol and 0.159 parts (0.025 % by volume) of 1,4-diaza- (2,2,2) -bicyclooctane at 65 ° -70 ° C. in the course of 3 hours. The reaction was then allowed to continue for 1/2 hour at 70 ° C. and the acetic acid introduced via the diketene was removed by stirring for 3 hours at 70 ° C. and 1 torr. A low-viscosity, clear oil is obtained which solidifies when inoculated. 1658 parts were obtained, which corresponds to a 97.4% yield.

Analysis Calculated 61.3% acetoacetyl
Found: 60.7 % acetoacetyl

Example 2 , _r

To 134 parts of trimethylolpropane and 0.034 parts (0.025% by weight) 1,4-Diaza- (2,2,2) -bicyclooctane were added dropwise to 254.5 parts of diketene at 60 ° -65 ° C. in the course of 90 minutes The mixture was subsequently stirred at this temperature for minutes

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the excess was in the thin-film evaporation at 65 ° C / 1 Torr

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on diketene and the acetic acid introduced over it. A practically colorless and low-viscosity product which was acid-free was obtained. 385 parts (yield 99.4 %) were obtained.

Analysis: Der .: 65.2 % acetoacetyl Found: 65.0 % acetoacetyl

Example 3

To 300 parts of a poxylated trimethylolpropane of the OH number 230 and 0.075 parts (0.025 wt%) 1,4-D.iaza ~ (2,2,2) -bicyclooctane 49.5 parts of pure diketene were added dropwise at 60 ° -65 ° C. in the course of 30 minutes, followed by more Was stirred for minutes at this temperature. A low-viscosity, almost colorless oil which was free from acetic acid was obtained and diketen v / ar. Yield: 348 parts (99.5%) of polyacetoacetic ester.

Analysis: Calc .: 25.6 % acetoacetyl Found: 24.8 % acetoacetyl

Example 4

169.9 parts of diketene were added dropwise at 65 ° -75 ° C. over the course of one hour to 200 parts of a propoxylated pentaerythritol with an OH number of 560 and 0.050 parts of 1,4-diaza- (2,2,2) -bicyclooctane. The mixture was then stirred at this temperature for 1/2 hour. The product was poured over a thin-film evaporator at 65 ° C./1 Torr. A low-viscosity, almost colorless oil which was free from acetic acid and diketene is obtained. Yield: 365 parts (92.0%) of polyacetoacetic ester.

Analysis: Calc .: 45.6 % acetoacetyl ;; ■; Found: 42.3% acetoacetyl:

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Example 5

To 200 parts of a branched polyester of OII number 102 from adipic acid, diethylene glycol and trimethylolpropane, 0.050 parts 1,4-PiaRa- (2,2,2) -bicyclooctane and 0.2 parts Glacial acetic acid, 30.5 parts of diketene were added dropwise at 65 ° C. in 1/2 hour and it became another hour at this temperature stirred. A moderately viscous golden yellow oil was obtained which was free from unreacted diketene. There were 227.5 parts Polyacctacetic ester obtained, which gives a yield of 98.5% corresponds to "the" theory.

Analysis: Der .: 13.2% acetoacetyl
Found: 12.1 % acetoacetyl

Example 6

To a mixture of 250 parts of a branched polyester the Oll number 145 and acid number 0.55 from adipic acid, phthalic acid, Diethylene glycol and trimethylolpropane, 0.050 part 1,4-diaza- (2,2,2) -bicyclooctane and 0.150 part glacial acetic acid 64.5 parts of diketene were added dropwise at 60 ° C. for 1/2 hour, after which the mixture was stirred at this temperature for 1/2 hour. Man received a moderately viscous oil which was free of unreacted diketene. Yield: 312 parts (99%) of polyacetoacetic ester. ■

Analysis: Calculated: 17.3 %. Acetoacetyl
Found: 16.4% acetoacetyl

Example 7

To 300 parts of an unsaturated, linear polyester Adipic acid, maleic acid and dibutylene glycol with an OH number of 87.0 and acid number 2.38 and 0.040 parts 1,4-diaza- (2,2,2) -bicyclooctane 39.0 parts of diketene were added dropwise at 60 ° C. over the course of 40 minutes. It was then held at this temperature for an additional 45 minutes stirred. A low-viscosity, golden-yellow, clear one was obtained

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oil that is free of unreacted biketen. Yield: 385 parts (98.9%) bisacetoacetic ester. .........

Analysis: Der .: 11.5 % acetoacetyl
Found 10.3 % acetoacetyl

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Claims (3)

P a t e η t a η s p r ü c he: 1) Method of making connections with two or more acetoacetic ester groups by reacting diketene with hydroxy compounds in the presence of tertiary amines, characterized in that aliphatic, cycloaliphatic or araliphatic © containing at least two hydroxyl groups Compounds in the presence of 0.0001 - 1 percent by weight, preferably 0.001-0.1 percent by weight, based on the amount of the hydroxyl compound used, 1,4-diaza- (2,2,2) -bicyclooctane Reacts in the absence of solvents. 2) Method according to claim 1, characterized in that one carries out the reaction at a temperature of between 20 ° and 120 ° C and preferably between 50 ° and 80 ⁰ C. 3) Method according to claim 1 and 2, characterized in that that the reaction is carried out in the presence of an organic acid performs.